Azo dyes derived from monoacylacetyl bodies and process of making same



Patented Aug. 3, 1926 ARTHUR 'zr'rscnna. or orrENmcn-on-rnE-main, GERMANY, ass'renon me I. e.

FABBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANKFOBT-ON-THE- MANY.

, GEE- AZO DYES DERIVED FROM MONOACYLACETYL BODIES AND PROCESS OF 1T0 Drawing. Application filed May 25, 1923, Serial No. 641,510, and in Germany November 11, 192R- My invention relates to new azo dyestufl's, lnsoluble ln water, of the general formula:

wherein Y means any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms, R an aryl residue, R an aromatic residue, and X an azo or azoxy group. Under the term an aromatic residue for R I include a carboor heterocyclic aromatic resideu, substituted or not, as Well the residue of an acyclic body, containing an acid methylene group, such its derivatives of the B-keton-aldehyde, e. g. acetylaceton, derivatives of the acetoacetic acid and the like.

The dyestuffs are when dry yeliow to brown powders, insoluble in water and soluble in sulfuric acid to a yellow to violet solution.

They can be used for the production of valuable pigment colors and give, when produced on the fiber, yellow to brown shades of a singular fastness to washing.

The new products are obtained by combining diazo-, tetrazoor diazoazocompounds, not containing a sulfonic or carboxylic group, with the corresponding acylacetylamino azoor -azoxybodies.

As diazocomponents I may use in this process those of anilin, its homologues and substitution products, such as toluidins, anisidins, chloroand nitroanilins, chlor oand nitrotoluidins, chloroand DItIOaDISIdIDS naphthylamins, aminoanthraquinones, aminoazocompounds, diaminobases such as d1anisidin, dichlorobenzidin diaminodiphenylether, diamino-azoand -azoxycompounds and others. I

The acylacetyl-aminoazoand -azoxybodies, not known hitherto, can be prepared by heating aminoazoor -azoxycompounds containin only one aminogroup, with acylacetic acid esters preferably in the presence of a solvent or diluent.

Among the aminoazo and ammoazoxy compounds suitable for the purpose of my present invention I may mention-am1noazobenzene and -toluene, aminoazoxybenzene,

the chlorinated and nitrated aminoazoben- The following examples illustrate the Il I 1- vention, the parts being by weight.

Example -1.

AHn t: 0 I

Production of the dyestufis on the fiber.

Example 2. I

The yarn, having been well boiled and dried, is impregnated with a solution of 10 gr. of acetoacetyl-4-aminoazobenzene or 10 also aminoazocomgr. of acetoacetyll-amino-3'-nitroazobenzone, 15 cc. of caustic soda solution of 34 B. and 20 cc. of Turkey red oil in the liter, well wrung out and without being dried, developed in a diazosolution, containing 3 gr. of 5-nitro-1.2-toluidin in the liter, to which is added sodium acetate.

In this manner I obtain with acetoacetyl- 4-aminoazobenzene yellow, with acetoacetyll-amino-3-nitroazobenzene reddish yellow clear tints of a very good fastness.

Example 3.

The yarn having been well boiled and dried, is impregnated with a solution of 10 gr. of acetoacetyl-4'-aminobenzene-azo-lphenyl-3-methyl-5-p razolon or 10 gr. of acetoacetyl-4'-amino enzene-azo-para-cresol, 15 cc. of caustic soda solution of 34 B and 20 cc. of Turkey red oil in the liter, well wrun out and, without being dried, developed in a diazo solution, containing 3 gr. of 5-chloro-L2-toluidin in the liter, to which is added sodium acetate.

With acetoacetyll' -aminobenzene-azo-1- phenyl-3-methyl-5-pyrazolon clear orange yellow, with acetoacetyl-i-aminobenzeneazo-para-cresol yellow tints of a very good fastness are obtained. The d estufi produced with acetoacetyl-4'-amino enzene-azo- 1-phenyl-3-methyl-5-pyrazolon probably has the formula:

In the same manner the process may be conducted with other diazocompounds and ,other corresponding acyl-acetyl-aminoazoor -azoxybodies, e. g. with benzoylacetic acid derivatives.

The following table gives some of the prepared a-n'minnnnthmnninnnn no-3-nitro-azobenzone. :10

Para-toluidln Acetoacetyl ortho l a-ammoanthraqumone aminoezotoluene. Orthwhlormnllln rln kclaloro-lfldoluidln. do 4-chloro-L2-anlsidin. do Ortho-nitroenllin do fi-nit o-LZ-fnlnidin do 4-nitro-l-nephthy do -Metaramlnoazotoluene do B-aminoenthraquinone ,Ortho-chloroanflim Acetoaoetyl 4 amino 1 phenylalanaphthalene. 4-chloro-L3'toluldln o 4-chloro-2-nitroenih do 5-nltro-L2-tolul in do Mete-aminoezotoluene do Orthohenetoldo napht ylemln. I Ortho-aminophenylether Acetoecetyl 4 -emlno-f-methyl-phenyl-ezo-l-naphthelene.

6-chloro-12-toluldin-.- do Ortho-nltroanilin do Ortho-chloroenllin Acetoecetyl 4'-amlnobenzene azo 3 methyl-l-phenyl- B-pyrazolon 2,5 flch1 rmnilln dn 2-chloro-4-njtroanllm do Ortho-njtrmnilin do Mhloro-1.2-toluidln Aeetoeeetyl-4-aml nobenzene szo 3- methyl-l-phenylo-pyrazolon (example 3). 4-nitro-L2-anisldln. Acetoacetyl 4'-amlnobenzene azo 3- methyl-l-phenylo-pyrazolon. S-nitro-LZ-toluldin do 4nitro-1-naphthyla.min do Ortho-aminoazotoluene lo Ortho-chloroanllin. Aoetoacetyl 4'-amlnobenzene ezo para-cresol. 2,54iich1omnnilln do 5-nitro-L2-tolul do 5-chloro-1.2-to1uldin Aoetoeeetyl 4-amlnobenzene azo pere-cresol (ex ample 0rtho-aminoezotoluene Acetoaoetyl Mami- Dlazooompound [rom- Comblned wlth- Shades.

Ortho-chloro-anllln AeetoecetYl-beml- Yellow.

. noazobenzene.

5-chloro-L2-toluldln..." do Yellow. 5-n1tro-1.2-toluidin Aoetoeeety] 4 ami- Yellow.

I noezobenzene (example 2). 4-nltro-1-naphthylamim. Acetoacetyl-4-aml- Olive-yellow.

noazobenzene. Ortho-emlnoazotoluene do Orange. a .nnthmnninnne dn Onmgeqellow. .Dlanisi ln do Yellowlsh brown. Ortho-amlnophenylether Aeetoacetyl-4-aml- Greemsh yellow.

noazoxybenzene. 6-nitro-L2-toluldln (In Lemon-yellow. 3-njtro-1 4 fnlnidin (In Yellgw, fl-amlnoanthmqninnn do Orangeyellow. Ortho-chloro-anllln Acetoaeetyl-4-aml- Yellow.

no-4-chloro-azopenzene (example 2.5-dichloroanllln Acetoecetyl-l-eml- Yellow 110-4 chloro ewbenzene. 4chloro-1.2-toluldin do Yellow. Ortho-mtroanilin do Yellow. 5-nitr -L2-fnlnirlin do Yellow. Ol'thn-nminmvnf mun (In Orange. fi-aminoanthrequinone.. do Orange-yellow. Ortho-chloroamlin Acetoeeetyl-4-ami- Yellow.

zene. 2.5dlchloroanilin do Yellow. 4-chloro-L2-toluidin do Yellow. Ortho-nitrmnilin (in Yellow. fi-nitro-lz toluidin Aeetoacetyl-4-ami- Reddlsh yellow.

zene (example 2). Ortho-eminoazotoluene. Acetoaeetyl-4-eml- H Orange-yellow. Yellow.

Yellow.

Yellow.

Yellow.

Reddlsh yellow.

Reddish yellow.

Browms' h -oliveyellow.

Olive-yellow.

Orange-yellow.

Reddish yellow.

Yellow.

Reddish yellow. 'Reddlsh yellow.

Redo A dleh yellow. Red'dish yellow. Orange-yellow.

Orange-yellow.

Orange. Yellowish brown. Brownish orange. Yellow.

Yellow. Beddish yellow. Yellow.

Orange.

Brownian orange.

When a diazocompound of dianisidin is combined with acetoacetyl--aminoazoben zone, the resulting dye stud probably has the formula:

When a diazocompound of B-aminoanthraquinone is combined with acetoacetyl-4- aminoazoxybenz'ene, the resulting dyestuif probably has the formula:

When a diazocompound of meta-aminoazotoluene is combined with acetoacetyllamino-'l-phenyl-azonaphthalin, the resulting dyestufi probably has the formula:

ill--11, M

5 When a diazocompound of ortho-aminophenylether is combined with acetoacetyl-4- amino-2-methyl phenyl azo-l-naphthalin, the resulting dyestuif probably has the formula:

on. I lo Jzn-n=n to o LHQM Ha When a diazocompoun-d of 4-nitro-1-naphthylamin is combined with acctoacetyl-4!- aminobenzene-azo-3methyl-l-phenyl 5 pyrazolon, the resulting dyestufi' probably has the formula:

HN===IN to I CH:0==NNC NHN===Ndn-oo I Now what I claim and desire to secure by Letters Patent is the following:

1. As new products the azodyestufis, insoluble in water, of the general formula:

wherein Y means any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms, R an aryl residue, R an aromatic residue, and X an azo or azoxy group, which are, when dry, yellow to brown powders, insoluble in water and soluble in sulfuric acid to a yellow to violet solution, said dyestuffs yielding valuable igment colors and, when produced on the fiber, yellow to brown shades of a singular fastness to washing. 1

2. A process of making azodyestufls, insoluble in water, consisting in combining diazocompounds not containing a sulfonic or carboxylic group with monoacylacetylbodies of the general formula:

.wherein Y means any radicle of the hydrocarbon series contalning at least one and not more than six carbon atoms R an aryl residue, R an aromatic residue and X an azo on azoxy grou 3. Textile mater ial dyed with one of the new azodyestufis as covered in claim 1, said dyestuff being developed on the material.

4. As new products the azodyestuffs, insoluble in water, of the general formula:

wherein Y means any radicle of the hydrocarbon series containing at least one and not more than six carbon atoms, R an aryl residue and R an aromatic residue, which are, when dry, yellow to brown powders, insoluble in water and soluble in sulfuric acid to a yellow to violet solution, said dyestuffs yielding valuable pigment colors and, when produced on the fiber, yellow to brown shades of a singular fastness to washing.

5. A process of making azodyestufl's, insoluble in water, consisting in combining diazocompounds not containing a sulfonic or carboxylic group with monoacylacetylbodies of the general formula:

wherein Y means any radicle of the hydrocarbon series containmg at least one and not more than six carbon atoms, R an aryl residue and R an aromatic residue;

6. Textile material dyed with one of the new azodyestufi's as covered in claim 4, said dyestufi being developed on the material.

' 7. As new products the azodyestufis, insoluble in water, of the general formula:-

wherein R means an aryl residue and R an aromatic residue.

9. Textile material dyed with one of the new azodyestufis as covered in claim 7, said dyestufi being developed on the material.

In testimony, that I claim the foregoing as my invention, I have signed my name, this 9th day of May 1923.

ARTHUR ZITSCHER. [L. 5.] 

